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Extraterrestrial Hydroxy Amino Acids in CM and CR Carbonaceous Chondrites

7 The abundances, distributions, and enantiomeric ratios of a family of three- and four- 8 9 10 carbon hydroxy amino acids (HAAs) were investigated in extracts of five CM and four 11 12 13 CR carbonaceous chondrites by gas chromatography-mass spectrometry (GC-MS) 14 15 16 analyses. Hydroxy amino acids were detected in both the acid hydrolysates of the hot 17 18 19 water extracts and the 6 M HCl extracts of all the CM and CR chondrites analyzed 20 21 22 here with total hot water and HCl extractable HAA concentrations ranging from 6.94 23 24 25 to 315 nmol per gram. The HAA analyses performed in this study revealed: 1) the 26 27 28 combined (hot water + HCl) extracts of CR2 chondrites contained greater abundances 29 30 31 of -HAAs than that of CM2 chondrites and 2) the combined extracts of CM and CR 32 33 34 chondrites contained roughly similar abundances of β- and γ-HAAs. Application of the 35 36 37 new GC-MS method developed here resulted in the first successful chromatographic 38 39 40 resolution of the enantiomers of an -dialkyl HAA, D,L--methylserine, in 41 42 43 carbonaceous chondrite extracts. Meteoritic -methylserine was found to be mostly 44 45 46 racemic within error and did not show L-enantiomeric excesses correlating with the 47 48 49 degree of aqueous alteration, a phenomenon observed in meteoritic isovaline, another 50 51 52 -dialkyl amino acid. The HAAs identified in CM and CR chondrite extracts could have 53 54 55 been produced during parent body alteration from the Strecker cyanohydrin reaction 56 57 58 (for -HAAs) and an ammonia-involved formose-like reaction (for β-, and γ-HAAs).

Amino acid(s), CM carbonaceous chondrite < Meteori↗

Aliphatic amines in the Murchison meteorite

The paper reports on the determination of aliphatic amines in water extracts of the Murchison meteorite. The amines were analyzed by gas chromatography both as the free amines and as 2,4-dinitrophenyl (DNP) derivatives. The results give evidence for the presence of all of the possible primary aliphatic monoamines (eight) with fewer than five carbon atoms. Two of the seven possible secondary or tertiary aliphatic monoamines were identified. The identified primary amines total 80 nmol per g meteorite, and seem to be chemically or physically trapped in the meteorite. Similarities between the water-extractable amines and amino acids suggest that (1) a simple carbon compound, methane, for example, is the precursor of meteorite amines and amino acids, and (2) both amines and amino acids are extracted from the meteorite both as such and in the form of acid-hydrolyzable derivative or precursor species.

Jungclaus, G.↗

Effect of salinity on the preservation of biomarkers in hypersaline microbial mat kerogens

Kerogen is the residue that remains after the minerals and organic compounds have been extracted from a rock using acid and organic solvents, respectively [1]. It is not only the largest organic carbon sink in the geological record but the best-preserved fraction due to its recalcitrance and ability to retain syngenetic source information during deposition [2]. Due to the complex, macromolecular, cross-linked polymeric structure of kerogen, it is difficult to analyse intact, often requiring breakdown into smaller subunits through thermal (pyrolysis) or chemical treatment (chemolysis) [3]. Saline and hypersaline environments host diverse microbial communities, which can trap and bind organic matrices such as cellular components (e.g., extracellular polymeric substances, cell wall, peptidoglycan, sheath material, etc.) with sediments, forming layered, laminated structures called microbial mats. Here we present depth profiles of two hypersaline cores through a microbial mat with differing total salinities. We looked at the composition of organic compounds released from kerogen during high temperature, hydrogen-assisted, pyrolysis to understand the effect of salinity on the composition and timing of their incorporation [4]. Field Site: The Exportadora del Sal S. A. (ESSA) saltern of Guerrero Negro (Baja California Sur, Mexico) lies within a typical sabhka environment adjacent to Laguna Ojo de Liebre. Note the spatial extent of the 13 major ponds of the ESSA system. The GN ponds thrive under well-monitored and stable conditions with steady state accretion and degradation of mat layers (around 0.5–1.4 cm per year). Organic mats typically attain up to 10 cm in thickness, depending on the location, which represents about 60 years of growth since these ponds were established. Sedimentation rate is rapid in these non-lithifying and non-mineralising mats, 1–1.5 cm per year. This environment is ideal for investigating in situ lipid preservation and diagenesis without the influence of constantly changing physical parameters. Methods: P4n5 and P5AB cores were collected as ~9 cm and 6.5 cm fresh cores, respectively, in June 2001 and September 2010, respectively from the ESSA saltern. The P4n5 core (9-9.1% salinity) was taken from Pond 4 near 5 and sub-divided into 10 layers. The P5AB core (11.2% salinity) was taken from Pond 5A near 5B and sub-divided into 8 layers. Lyophilised microbial mat powders were solvent-extracted using a modified Bligh-Dyer method and analysed by gas chromatography-mass spectrometry (GC-MS). Additionally, a subset of layers—layer 4 and layer 7—which represented active biomass and sediment-processed, respectively, were subjected to mild-acid methanolysis. The respective residues from conventional solvent extraction and acid methanolysis were loaded with a molybdenum sulfide catalyst and placed into a stainless-steel reactor. Samples were run on the hydropyrolysis set up (heated to 500 °C with 13-15 MPa of H2 pressure), extracted, and analysed by GC-MS. Results: Molecular profiles from the two ponds were significantly different and reflect the contributions of different photosynthetic and respiratory microbial communities to preserved organic matter. For example, the higher salinity P5AB core showed evidence of greater archaeal inputs (similarly observed in lab culture experiments [5]) as well as potential kerogen-bound carotenoids/carotenoid rearranged products or fragments. A hydrophobic emulsion formed during the acid methanolysis processing of layer 4 from both P4n5 and P5AB and layer 7 of P5AB. Hydropyrolysis of this hydrophobic residues released a greater abundance of polycyclic lipids relative to the pre-extracted control. Implications and Future Work: Catalytic hydropyrolysis of kerogen can rapidly generate abundant saturated pyrolysate products from the bound biomarker pool without altering the structures or stereochemistries of the products [6]. Chemical processing of solvent-extractable residues indicated that cellular matrices such as extracellular polymeric substances (EPS) may play a role in the sequestration of polycyclic lipid biomarkers such as steranes and hopanes. Their higher relative abundance compared to the pre-extracted control in the higher salinity layers and cores preliminarily aligns with this hypothesis, although further experiments are required to confirm this. It has been well-documented that EPS plays an important role in mineralisation, specifically carbonate formation, in microbial ecosystems. EPS can enhance calcium carbonate precipitation by providing diffusion-limited sites that create alkalinity gradients in response to microbial processes [7]. It has been experimentally demonstrated that salinity influences the total amount of EPS (both loosely- and tightly-bound) which increases with increasing salinity [8]. The higher salinity at Guerrero Negro switches the microbial population from filamentous Microcoleus to being dominated by Phormidium, Oscillatoria, and unicellular cyanobacteria. We demonstrated that lipid binding into kerogen via strong covalent linkages occurs at the very earliest stages of sedimentary diagenesis. We are currently investigating the influence of salinity on organic preservation through experimental and modelling approaches. Understanding how key biomarkers transform into preserved organic matter (i.e., from precursor biolipids to bound geolipids) in brine ecosystems will aid the search for organic biosignatures on other planetary bodies, especially Icy Moons and modern Mars.

hypersaline↗

Relative Amino Acid Concentrations as a Signature for Parent Body Processes of Carbonaceous Chondrites

Most meteorites are thought to have originated from objects in the asteroid belt. Carbonaceous chondrites, which contain significant amounts of organic carbon including complex organic compounds, have also been suggested to be derived from comets. The current model for the synthesis of organic compounds found in carbonaceous chondrites includes the survival of interstellar organic compounds and the processing of some of these compounds on the meteoritic parent body. The amino acid composition of five CM carbonaceous chondrites, two CIs, one CR, and one CV3 have been measured using hot water extraction-vapor hydrolysis, OPA/NAC derivatization and high-performance liquid chromatography (HPLC). Total amino acid abundances in the bulk meteorites as well as the amino acid concentrations relative to glycine = 1.0 for beta-alanine, alpha-aminoisobutyric acid and D-alanine were determined. Additional data for three Antarctic CM meteorites were obtained from the literature. All CM meteorites analyzed in this study show a complex distribution of amino acids and a high variability in total concentration ranging from approx. 15,300 to approx. 5800 parts per billion (ppb), while the CIs show a total amino acid abundance of approx. 4300 ppb. The relatively (compared to glycine) high AIB content found in all the CMs is a strong indicator that Strecker-cyanohydrin synthesis is the dominant pathway for the formation of amino acids found in these meteorites. The data from the Antarctic CM carbonaceous chondrites are inconsistent with the results from the other CMs, perhaps due to influences from the Antarctic ice that were effective during their residence time. In contrast to CMs, the data from the CI carbonaceous chondrites indicate that the Strecker synthesis was not active on their parent bodies.

Botta, Oliver↗

[Stardust Amines]

We investigated the abundances of amino acids and amines, as well as their enantiomeric composition in water extracts of comet Wild 2 exposed aerogel and aluminum foils returned by Stardust using liquid chromatography with UV fluorescence detection and time of flight-mass spectrometry (LC-FD/ToF-MS). A suite of amino acids and amines including glycine, L-alanine, methylamine (MA), and ethylamine (EA) were identified in the Stardust bulk aerogel. With the exception of MA and EA, all other primary amines detected in comet-exposed aerogels were also present in the aerogel witness tile that was not exposed to Wild 2, suggesting that most amines are terrestrial in origin. The enhanced abundances of MA, EA, and possibly glycine in comet-exposed aerogel compared to controls, coupled with MA to EA ratios (approx.1 to 2) that are distinct from preflight aerogels (approx.7 to lo), suggest that these amines were captured from Wild 2. The presence of cometary amines in Stardust material supports the hypothesis that comets were an important source of prebiotic organics on the early Earth. To better understand their origin, a systematic study of all these species with C, N, and H compound specific isotopic analysis (CSIA) via gas chromatography quadrupole mass spectrometry in with parallel with combustion isotope ratio mass spectrometry (GC-QMS/IRMS) is being conducted. We will discuss our latest C-CSIA measurements and what they indicate about the origin of the amino acids extracted from Stardust samples.

Dworkin, Jason P.↗

Amino Acid Chemistry as a Link Between Small Solar System Bodies and Carbonaceous Chondrites

Establishing chemical links between meteorites and small solar system bodies, such as comets and asteroids, provides a tool for investigating the processes that occurred during the formation of the solar system. Carbonaceous meteorites are of particular interest, since they may have seeded the early Earth with a variety of prebiotic organic compounds including amino acids, purines and pyrimidines, which are thought to be necessary for the origin of life. Here we report the results of high-performance liquid chromatography (HPLC) based amino acid analyses of the acid-hydrolyzed hot water extracts from pristine interior pieces of the CI carbonaceous chondrites Orgueil and Ivuna and the CM meteorites Murchison and Murray. We found that the CI meteorites Orgueil and Ivuna contained high abundances of beta-alanine and glycine, while only traces of other amino acids like alanine, alpha-amino-n-butryic acid (ABA) and alpha-aminoisobutyric acid (AIB) were detected in these meteorites. Carbon isotopic measurements of beta-alanine and glycine in Orgueil by gas chromatography combustion-isotope ratio mass spectrometry clearly indicate an extraterrestrial origin of these amino acids. The amino acid composition of Orgueil and Ivuna was strikingly different from the CM chondrites Murchison and Murray. The most notable difference was the high relative abundance of B-alanine in Orgueil and Ivuna compared to Murchison and Murray. Furthermore, AIB, which is one of the most abundant amino acids found in Murchison and Murray, was present in only trace amounts in Orgueil and Ivuna. Our amino acid data strongly suggest that the CI meteorites Orgueil and Ivuna came from a different type of parent body than the CM meteorites Murchison and Murray, possibly from an extinct comet. It is generally thought that carbonaceous meteorites are fragments of larger asteroidal bodies delivered via near Earth objects (NEO). Orbital and dynamic studies suggest that both fragments of main belt asteroids and comets replenish the NEO population, therefore extinct comets may contribute up to half of all NEO's. A comparison of an amino acid analysis of a returned NEO sample to CI and CM carbonaceous chondrites would help establish a link between small solar system bodies and meteorites. Based on our amino acid measurements of CI and CM chondrites, amino acid chemistry can be included as an additional set of criteria to constrain the nature of meteorite parent bodies.

Glavin, Daniel P.↗

A new technique for collection, concentration and determination of gaseous tropospheric formaldehyde

This article describes an improved technique for making in situ measurements of gaseous tropospheric formaldehyde (CH2O). The new technique is based on nebulization/reflux principles that have proved very effective in quantitatively scrubbing water soluble trace gases (e.g., CH2O) into aqueous mediums, which are subsequently analyzed. Atmospheric formaldehyde extractions and analyses have been performed with the nebulization/reflux concentrator using an acidified dinitrophenylhydrazine solution that indicate that quantitative analysis of CH2O at global background levels (about 0.1 ppbv) is feasible with 20-min extractions. Analysis of CH2O, once concentrated, is accomplished using high performance liquid chromatography with ultraviolet photometric detection. The CH2O-hydrazone derivative, produced by the reaction of 2,4-dinitrophenylhydrazine in H2SO4 acidified aqueous solution, is detected as CH2O.

Cofer, W. R., III↗

Amino acids of the Murchison meteorite. III - Seven carbon acyclic primary alpha-amino alkanoic acids

All of the eighteen possible seven-carbon acyclic primary alpha-amino alkanoic acids have been positively identified in a hot-water extract of the Murchison meteorite by the combined use of gas chromatography-mass spectrometry, ion exchange chromatography and reversed-phase chromatography. None of these amino acids has previously been found in meteorites or in any other natural material. They range in concentration from less than or equal to 0.5 to 5.3 nmol/g. Configuration assignments were made for 2-amino-3,4-dimethylpentanoic acid and allo-2-amino-3,4-dimethylpentanoic acid and the diasteromer ratio was determined. Fifty-five amino acids have now been positively identified in the Murchison meteorite, 36 of which are unknown in terrestrial materials. This unique suite of amino acids is characterized by the occurrence of all structural isomers within the two major classes of amino acids represented, by the predominance of branched chain isomers, and by an exponential decline in amount with increasing carbon chain length within homologous series. These characteristics of the Murchison amino acids are suggestive of synthesis before incorporation into a parent body.

Cronin, John R.↗

Determination of low molecular weight thiols using monobromobimane fluorescent labeling and high-performance liquid chromatography

Methods are described for the preparation and high-performance liquid chromatography (HPLC) analysis of monobromobimane derivatives of low molecular weight thiols in extracts of biological samples. Typical problems encountered in the development and application of these methods are discussed. Analysis of mung bean extract is used as an example.

Fahey, Robert C.↗

Phenols in hydrothermal petroleums and sediment bitumen from Guaymas Basin, Gulf of California

The aliphatic, aromatic and polar (NSO) fractions of seabed petroleums and sediment bitumen extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry (free and silylated). The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolyzates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore sediments are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds in samples with a high degree of thermal maturity. Phenols are one class of oxygenated compounds found in these samples. A group of methyl-, dimethyl- and trimethyl-isoprenoidyl phenols (C27-C29) is present in all of the seabed NSO fractions, with the methyl- and dimethyl-isoprenoidyl phenols occurring as major components, and a trimethyl-isoprenoidyl phenol as a minor component. A homologous series of n-alkylphenols (C13-C33) has also been found in the seabed petroleums. These phenols are most likely derived from the hydrothermal alteration of sedimentary organic matter. The n-alkylphenols are probably synthesized under hydrothermal conditions, but the isoprenoidyl phenols are probably hydrothermal alteration products of natural product precursors. The suites of phenols do not appear to be useful tracers of high temperature hydrothermal processes.

Non-NASA Center↗

Parent Body Influences on Amino Acids in the Tagish Lake Meteorite

The Tagish Lake meteorite is a primitive C2 carbonaceous chondrite with a mineralogy, oxygen isotope, and bulk chemical. However, in contrast to many CI and CM carbonaceous chondrites, the Tagish Lake meteorite was reported to have only trace levels of indigenous amino acids, with evidence for terrestrial L-amino acid contamination from the Tagish Lake meltwater. The lack of indigenous amino acids in Tagish Lake suggested that they were either destroyed during parent body alteration processes and/or the Tagish Lake meteorite originated on a chemically distinct parent body from CI and CM meteorites where formation of amino acids was less favorable. We recently measured the amino acid composition of three different lithologies (11h, 5b, and 11i) of pristine Tagish Lake meteorite fragments that represent a range of progressive aqueous alteration in order 11h < 5b < 11i as inferred from the mineralogy, petrology, bulk isotopes, and insoluble organic matter structure. The distribution and enantiomeric abundances of the one- to six-carbon aliphatic amino acids found in hot-water extracts of the Tagish Lake fragments were determined by ultra performance liquid chromatography fluorescence detection and time of flight mass spectrometry coupled with OPA/NAC derivatization. Stable carbon isotope analyses of the most abundant amino acids in 11h were measured with gas chromatography coupled with quadrupole mass spectrometry and isotope ratio mass spectrometry.

Glavin, D. P.↗

Characteristics of In Situ Fine Fraction Aerosol Spectra from 300-700 nm Observed Around the Korean Peninsula During KORUS-OC

In situ aerosol extinction and absorption spectra covering the 300-700 nm range at ≤ 1 nm spectral resolution were measured aboard the R/V Onnuri during the Korea U.S. – Ocean Color (KORUS-OC) cruise around the Korean Peninsula from May 21 through June 3, 2016. Total absorption spectra were obtained from aerosols collected on glass fiber filters and subsequently placed in the center of an integrating sphere (Labsphere DRA-CA-30) attached to a dual beam spectrophotometer (Cary 100 Bio UV-Visible Spectrophotometer, 0.2 nm spectral resolution). Absorption spectra from methanol and deionized water extracts of aerosols collected on Teflon filters were measured in a liquid waveguide capillary cell (World Precision Instruments LWCC- 3100, ~0.4 nm spectral resolution). Extinction spectra were measured with a custom built instrument (SpEx, ~0.8 nm spectral resolution). The measurements were obtained at a height of ~10 m above the sea surface with an inlet that limited the measured aerosols to diameters ≤ 1.3 µm. All four sets of spectra exhibit curvature in log-log space with 2nd order polynomials providing a better fit to the measured spectra than power law fits. The deionized water extracts were also analyzed with an ion chromatograph (Dionex ICS-3000 Ion Chromatography System) and with an aerosol mass spectrometer (Aerodyne Research, Inc. HR-ToF High Resolution Aerosol Mass Spectrometer) to examine chemical composition. These data indicate the optical spectra are sensitive to differing chemical properties of the measured ambient aerosols and suggest differing sources and/or atmospheric processes influence the observed optical signatures. The measured suite of spectra are combined to examine the spectral characteristics of single scattering albedo, as well as to examine the contribution of soluble absorbing chromophores to the total absorption spectra. Additional measurements made during the affiliated Korea U.S. - Air Quality (KORUS-AQ) campaign will be used to provide further insight on the observed spectral characteristics.

Jordan, Carolyn E↗

Non-Protein Amino Acids Identified in Carbon-Rich Hayabusa Particles

Amino acid abundances in acid-hydrolyzed hot water extracts of gold foils containing five Category 3 (carbon-rich) Hayabusa particles were studied using liquid chromatography with tandem fluorescence and accurate mass detection. Initial particle analyses using field emission scanning electron microscopy with energy-dispersive X-ray spectrometry indicated that the particles were composed mainly of carbon. Prior to amino acid analysis, infrared and Raman microspectroscopy showed some grains possessed primitive organic carbon. Although trace terrestrial contamination, namely L-protein amino acids, was observed in all Hayabusa extracts, several terrestrially uncommon non-protein amino acids were also identified. Some Hayabusa particles contained racemic (D≈L) mixtures of the non-protein amino acids β-aminoisobutyric acid (β-AIB) and β-amino-n-butyric acid (β-ABA) at low abundances ranging from 0.09 to 0.31 nmol g −1 . Larger abundances of the non-protein amino acid β-alanine (9.2 nmol g −1 , ≈4.5 times greater than background levels) were measured in an extract of three Hayabusa particles. This β-alanine abundance was ≈6 times higher than that measured in an extract of a CM2 Murchison grain processed in parallel. The comparatively high β-alanine abundance is surprising as asteroid Itokawa is similar to amino acid-poor LL ordinary chondrites. Elevated β-alanine abundances and racemic β-AIB and β-ABA in Hayabusa grains suggested these compounds have non-biological and plausibly non-terrestrial origins. These results are the first evidence of plausibly extraterrestrial amino acids in asteroid material from a sample-return mission and demonstrate the capabilities of the analytical protocols used to study asteroid Ryugu and Bennu samples returned by the JAXA Hayabusa2 and NASA OSIRIS-REx missions, respectively.

Eric T. Parker↗

Quantification of monocarboxylic acids in the Murchison carbonaceous meteorite

The abundances of some of the straight- and branched-chain isomers of the monocarboxylic acids found in the Murchison carbonaceous chondrite are determined. Monocarboxylic acids extracted from a crushed sample of Murchison interior were quantified by means of gas chromatography and mass spectroscopy after a spiking solution of deuterated analogues of 11 carboxylic acids had been added. Monocarboxylic acid abundances are found to range between 1.83 and 0.01 micromole/g, which is significantly higher than Murchison amino acid concentrations, and to decrease with increasing carbon number for both branched and unbranched molecules. The results are interpreted to support the abiotic extraterrestrial synthesis of monocarboxylic acids. Possible mechanisms leading to the equal synthesis of branched and each unbranched carboxylic acid with the same carbon number are considered, noting that the Fischer-Tropsch Type mechanism by itself is incapable of accounting for the observed distributions.

Lawless, J. G.↗

Recovery of precious metals from space

The overall objective is to develop efficient and economical separation and recovery methods for the platinum group and other precious metals. The separation of Pd(II) from Pt(II), Ir(III), and Rh(III) with trioctylphosphine oxide (TOPO) in heptane using centrifugal partition chromatography (CPC) was investigated. Activities to achieve this objective focussed on selection and evaluation of extraction systems for the PGM and modification of selected systems for multistage operation with a view to scaling up to desired macro levels. On the basis of preliminary evaluation of a series of simple metal complexing agents and chelating agents, the TOPO in heptane was selected as a likely system for isolating of Pd(II) and Pt(II) from the other PGM. A multistage apparatus capable of configuration as a simple rugged device, a centrifugal partition chromatograph (CPC), was shown to be effective. The extraction of Pd(II) was studied by CPC and batch solvent extraction. The distribution ratios for Pd(II) determined by both methods agree well. In low HCl concentrations (less than 0.1 M), the extracted species was PdCl2.(TOPO)2, irrespective of the chloride concentration, while at acid concentrations above 0.1 M, the Pd was extracted as the ion pair, 2(TOPO.H+).(PdCl4)2-. Base line separation of Pd(II) and Pt(II) in CPC was obtained under a variety of chloride and HCl concentration. It was demonstrated that the efficiency of CPC for metal separation was limited by chemical kinetic factors rather than instrumental factors, strongly suggesting that dramatic improvements can be achieved by studying reaction kinetics of formation and dissociation of the extractable metal complex.

Freiser, Henry↗

Detection of Cometary Amines in Samples Returned by the Stardust Spacecraft

The delivery of amino acids to the early Earth by comets and their fragments could have been a significant source of the early Earth's prebiotic organic inventory that led to the emergence of life (Chyba and Sagan, 1992). Over 20 organic molecules including methane, ethane, ammonia, cyanic acid, formaldehyde, formamide, acetaldehyde, acetonitrile, and methanol have been identified by radio spectroscopic observations of the comae of comets Hale-Bopp and Hyakutake (Crovisier et al. 2004). These simple molecules could have provided the organic reservoir to allow the formation of more complex prebiotic organic compounds such as amino acids. After a 7-year mission, the Stardust spacecraft returned to Earth samples from comet Wild 2 on January 15, 2006 providing the opportunity to analyze the organic composition and isotopic distribution of cometary material with state-of-the-art laboratory instrumentation. The Preliminary Examination Team analyses of organics in samples returned by Stardust were largely focused on particles that impacted the collector aerogel and aluminum foil (Sandford et al. 2006). However, it is also possible that Stardust returned a "diffuse" sample of gas-phase organic molecules that struck the aerogel directly or diffused away from the grains after impact. To test this possibility, samples of Stardust flight aerogel and foil were carried through a hot water extraction and acid hydrolysis procedure to see if primary amine compounds were present in excess of those seen in controls. Here we report highly sensitive liquid chromatography time-of-flight mass spectrometry measurements of amino acids and amines in samples returned from a comet (Glavin et al. 2008). A suite of amino acids and amines including glycine, L-alanine, methylamine (MA), and ethylamine (EA) were identified in the Stardust bulk aerogel. With the exception of MA and EA, all other primary amines detected in comet-exposed aerogels were also present in the aerogel witness tile that was not exposed to Wild 2, suggesting that most amines are terrestrial in origin. However, the enhanced abundances of MA, EA, and possibly glycine in comet-exposed aerogel compared to controls, coupled with MA to EA ratios (1 to 2) that are distinct from preflight aerogels (7 to 10), suggest that these amines were captured from Wild 2. It is possible that MA and EA were formed on energetically processed icy grains containing methane, ethane, and ammonia. The presence of cometary amines in Stardust material supports the hypothesis that comets were an important source of prebiotic organics on the early Earth. To better understand their origin, a systematic compound specific carbon isotopic analysis (C-CSIA) via gas chromatography quadrupole mass spectrometry in with parallel with combustion isotope ratio mass spectrometry (GCQMS/ IRMS) is being conducted. We will discuss our latest C-CSIA measurements and what they indicate about the origin of amino acids extracted from Stardust samples.

Glavin, Daniel P.↗

Detection of Cometary Amines in Samples Returned by the Stardust Spacecraft

The delivery of amino acids to the early Earth by comets and their fragments could have been a significant source of the early Earth's prebiotic organic inventory that led to the emergence of life (Chyba and Sagan, 1992). Over 20 organic molecules including methane, ethane, ammonia, cyanic acid, formaldehyde, formamide, acetaldehyde, acetonitrile, and methanol have been identified by radio spectroscopic observations of the comae of comets Hale-Bopp and Hyakutake (Crovisier et al. 2004). These simple molecules could have provided the organic reservoir to allow the forn1ation of more complex prebiotic organic compounds such as amino acids. After a 7 -year mission, the Stardust spacecraft returned to Earth samples from comet Wild 2 on January 15, 2006 providing the opportunity to analyze the organic composition and isotopic distribution of cometary material with state-of-the-art laboratory instrun1entation. The Preliminary Examination Team analyses of organics in samples returned by Stardust were largely focused on particles that impacted the collector aerogel and aluminum foil (Sandford et al. 2006). However, it is also possible that Stardust returned a "diffuse" sample of gas-phase organic molecules that struck the aerogel directly or diffused away from the grains after impact. To test this possibility, samples of Stardust flight aerogel and foil were carried through a hot water extraction and acid hydrolysis procedure to see if primary amine compounds were present in excess of those seen in controls. Here we report highly sensitive liquid chromatography time-of-flight mass spectron1etry measurements of amino acids and amines in samples returned from a comet (Glavin et al. 2008). A suite of amino acids and amines including glycine, L-alanine, methylamine (MA), and ethylamine (EA) were identified in the Stardust bulk aerogel. With the exception of MA and EA, all other primary amines detected in comet-exposed aerogels were also present in the aerogel witness tile that was not exposed to Wild 2, suggesting that most amines are terrestrial in origin. However, the enhanced abundances of MA, EA, and possibly glycine in comet-exposed aerogel compared to controls, coupled with MA to EA ratios (1 to 2) that are distinct from preflight aerogels (7 to 10), suggest that these amines were captured from Wild 2. It is possible that MA and EA were formed on energetically processed icy grains containing methane, ethane, and ammonia. The presence of cometary amines in Stardust material supports the hypothesis that comets were an important source of pre biotic organics on the early Earth. To better understand their origin, a systematic compound specific carbon isotopic analysis (C-CSIA) via gas chromatography quadrupole mass spectrometry in with parallel with combustion isotope ratio mass spectrometry (GC-QMS/IRMS) is being conducted. We will discuss our latest C-CSIA measurements and what they indicate about the origin of amino acids extracted from Stardust samples.

Glavin, Daniel P.↗